This paper describes both the synthesis and characterization of a biobased and non-aromatic polyacetal produced from the reaction between isosorbide and methylene chloride. The reaction was conducted in an aprotic dipolar and harmless solvent using a one-step, fast and economical procedure. The chemical composition of this polymer was investigated using Nuclear Magnetic Resonance and Fourier Transform Infra-Red spectroscopies. The molecular weights were examined by size exclusion chromatography and MALDI-TOF spectrometry. The synthesis conditions (concentration, mixing speed, solvent nature, stoichiometry, addition mode of one reactan) were found to strongly influence both polymer architecture and reaction yield. Under moderated stirring conditions, the polyacetal was characterized by a larger amount of macro-cycles. Inversely, under higher intensity mixing and with an excess of methylene chloride, it was mainly composed of linear chains. In this latter case, the polymeric material presented an amorphous morphology with a glass transition temperature (T_g) close to 55 °C. Its degradation temperature was evaluated to be close to 215 °C using thermogravimetry according to multi-ramp methodology. The chemical approach and the physicochemical properties are valuable in comparison with that characteristic of other isosorbide-based polyacetals.

This study provides a comprehensive quantitative comparison of three structurally distinct epoxy prepolymers—cycloaliphatic, novolac, and bis-aromatic (BADGE)—cured with a single hardener, methyl nadic anhydride (MNA), and catalyzed by 1-methylimidazole under strictly identical stoichiometric and thermal conditions. Each formulation was optimized in terms of epoxy/anhydride ratio and catalyst concentration to ensure meaningful cross-comparison under representative cure conditions. A multi-technique approach combining differential scanning calorimetry (DSC), dynamic rheometry, and thermogravimetric analysis (TGA) was employed to jointly assess cure kinetics, network build-up, and long-term thermal stability. DSC analyses provided reaction enthalpies and glass transition temperatures (Tg) ranging from 145 °C (BADGE-MNA) to 253 °C (cycloaliphatic ECy-MNA) after stabilization of the curing reaction under the chosen thermal protocol, enabling experimental fine-tuning of stoichiometry beyond the theoretical 1:1 ratio. Isothermal rheology revealed gel times of approximately 14 s for novolac, 16 s for BADGE, and 20 s for the cycloaliphatic system at 200 °C, defining a clear hierarchy of reactivity (Novolac > BADGE > ECy). Post-cure thermomechanical performance and thermal aging resistance (100 h at 250 °C) were assessed via rheometry and TGA under both dynamic and isothermal conditions. They demonstrated that the novolac-based resin retained approximately 93.7% of its initial mass, confirming its outstanding thermo-oxidative stability. The three systems exhibited distinct trade-offs between reactivity and thermal resistance: the novolac resin showed superior thermal endurance but, owing to its highly aromatic and rigid structure, limited flowability, while the cycloaliphatic resin exhibited greater molecular mobility and longer pot life but reduced stability. Overall, this work provides a comprehensive and quantitatively consistent benchmark, consolidating stoichiometric control, DSC and rheological reactivity, Tg evolution, thermomechanical stability, and degradation behavior within a single unified experimental framework. The results offer reliable reference data for modeling, formulation, and possible use of epoxy–anhydride thermosets at temperatures above 200 °C.